Detergent compositions or components comprising hydrophobically modified cellulosic polymers

ABSTRACT

The present invention relates to detergent compositions or components comprising certain cyclic amine based polymers and certain anionic cellulose materials. This combination imparts improved appearance and integrity benefits to fabrics and textiles laundered in washing solutions formed from such compositions, whilst also providing improved whiteness and/or brightness maintenance.

This application claims the benefit of provisional application No.60/103,978 filed Oct. 13, 1998 and 60/148,053 filed Aug. 10, 1999.

TECHNICAL FIELD

The present invention relates to detergent compositions or componentscomprising a specific hydrophobically modified cellulosic polymer andone or more quatemary ammonium compounds.

BACKGROUND OF THE INVENTION

It is known that fabrics and textiles simply wear out over time and withuse. Also, the laundering of the fabrics and textiles, over many cycles,can accentuate and contribute to the deterioration of the integrity andthe appearance of such fabrics and textiles. Deterioration of fabricintegrity and appearance can manifest itself in several ways. Forexample, short fibers are dislodged from woven and knit fabric/textilestructures by the at mechanical action of laundering. These dislodgedfibers may form lint, fuzz or “pills” which are visible on the surfaceof fabrics and diminish the appearance of newness of the fabric.Further, repeated laundering of fabrics and textiles, especially withbleach-containing laundry products, can remove dye from fabrics andtextiles and impart a faded, worn out appearance as a result ofdiminished color intensity, and in many cases, as a result of changes inhues or shades of color.

Given the foregoing, there is clearly an ongoing need to identifymaterials which could be added to laundry detergent products that wouldassociate themselves with the fibers of the fabrics and textileslaundered using such detergent products and thereby reduce or minimizethe tendency of the laundered fabric/textiles to deteriorate inappearance. Any such detergent product additive material should, ofcourse, be able to benefit fabric appearance and integrity withoutunduly interfering with the ability of the laundry detergent to performits fabric cleaning function. Co-pending applications PCT/US98/19139describes the use of hydrophobically modified cellulosic polymers whichare found to provide excellent integrity benefits to fabrics.

The inventor has now found that when these hydrophobically modifiedcellulosic polymers are used in combination specific cationicallycharged compounds, namely having a quaternary ammonium group, such asspecific quaternary ammonium surfactants, softeners and dispersants, thefabric care and fabric integrity can be further improved. Furthermore,the performance of the quaternary ammonium compound is improved, e.g. ansurprisingly improved cleaning and/or softening and/or soil removal orwhiteness or brightness maintenance is achieved when these materials areused together. It is also found that when the cellulosic material andthe quatemary ammonium compound or compounds are present in an intimatemixture, such as in the form of an agglomerate, a compacted granule or aspray dried granule, these benefits are even more apparent.

It is believed that these benefits are achieved because the specificcellulosic material and the specific cationic compounds having aquatemary ammonium group, interact in such a manner that both materialsenhance each others surface activity, resulting in a better interactionwith or deposition onto the surface of the fabric. This then will resultin improved performance of not only the cellulosic polymer, but also thequaternary ammonium compound, thus, an improved fabric integrity andimproved cleaning, softening and/or soil removal or whiteness/brightnessmaintenance results. It is believed that when the cellulosic polymersand quaternary ammonium compound or compounds are present in an intimatemixture, e.g. in the same component or granule, this interaction betweenthe materials is even more likely to occur or even stronger, resultingin even greater benefits

SUMMARY OF THE INVENTION

The present invention relates to a detergent composition or component,or additive comprising:

a) from 0.01% to 90% by weight, preferably form 0.05% to 50% by weight,of a salt of a quaternary ammonium compound; and

b) from 0.01% to 90% by weight, preferably from about 0.05% to about 20%by weight of a hydrophobically modified cellulosic polymer.

The compositions may be laundry detergents or additives, fabricsofteners or fabric treatment products. The components can be containedin these compositions. The present invention also relates to thelaundering or treating of fabrics and textiles in aqueous washing ortreating solutions formed from effective amounts of the detergentcompositions or components described herein, or formed from theindividual polymeric materials of such compositions or components.Laundering of fabrics and textiles in such washing solutions impartsfabric appearance benefits to the fabric and textile articles sotreated. Such benefits can include improved overall appearance,pill/fuzz reduction, antifading, improved abrasion resistance, and/orenhanced softness and also improved whiteness and/or brightnessmaintenance or even improved cleaning performance.

The cationic compounds and the cellulose material are preferably in anintimate mixture with one another. In one preferred embodiment, thecompounds are intimately mixed prior to introduction to the compositionor component of the invention.

Preferably, the mixture is present in an agglomerated, compacted orspray-dried particle, when the composition or component is solid.

Hereby it may be preferred that the compounds are mixed with an anionicsurfactant, preferably LAS, as described herein after. It may also bepreferred that a hydrotrope is admixed to this mixture, preferably STS.Also preferred in the mixture are inorganic and/or organic salts andacids and/or silicates or aluminosilicates, including zeolite, amorphoussilicates, crystalline (layered) silicates, carbonate, bicarbonate,phosphate, citric acid, malic acid, maleic acid, tartaric acid or saltsthereof, or mixtures of these ingredients.

DETAILED DESCRIPTION OF THE INVENTION Hydrophobically ModifiedCellulosic Based Polymers

The hydrophobically modified cellulosic polymers herein includepolymers, oligomers, copolymers and also cross-linked polymers,oligomers and copolymers. The will herein be referred to as cellulosicbased polymers. As will be apparent to those skilled in the art, anoligomer is a molecule consisting of only a few monomer units whilepolymers comprise considerably more monomer units. For the presentinvention, oligomers are defined as molecules having an averagemolecular weight below about 1,000 and polymers are molecules having anaverage molecular weight of greater than about 1,000. One suitable typeof cellulosic based polymer herein has an average molecular weight offrom about 5,000 to about 2,000,000, preferably from about 50,000 toabout 1,000,000.

Depending on the application of the composition or component herein, theamount of cellulosic based polymers in the compositions or componentsmay very. The cellulosic based polymers will generally be about 0.01% toabout 90% by the weight of the detergent composition or component, morepreferably from 0.05% to 20% or even from 0.05% to 15% by weight. Indetergent compositions herein it may for example be preferred that thepolymer is present at a level of from 0.05% to 10% by weight of thedetergent composition, preferably from 0.05% to 5% or even from 0.05% to3% or even 0.1% to 2% by weight. In detergent additives or components,the polymer may preferably be present at a level of 0.05% to 40% byweight of the component, or even from 0.05% to 20% or even 0.1% to 15%or even 1% to 10% by weight.

The cellulosic based polymers herein is preferably present in thecomposition or component in such an amount that the concentration ofpolymer in the wash is from 100 ppm to 10,000 ppm, preferably from 500ppm to 7000 ppm or even from 1000 to about 3000 ppm.

The cellulosic based polymer for use herein is preferably of thefollowing formula:

wherein each R is selected from the group consisting of R₂, R_(C), and

wherein:

each R₂ is independently selected from the group consisting of H andC₁-C₄ alkyl;

each R_(C) is

 wherein each Z is independently selected from the group consisting ofM, R₂, R_(C), and R_(H);

each R_(H) is independently selected from the group consisting of C₅-C₂₀alkyl, C₅-C₇ cycloalkyl, C₇-C₂₀ alkylaryl, C₇-C₂₀ arylalkyl, substitutedalkyl, hydroxyalkyl, C₁-C₂₀ alkoxy-2-hydroxyalkyl, C₇-C₂₀alkylaryloxy-2-hydroxyalkyl, (R₄)₂N-alkyl, (R₄)₂N-2-hydroxyalkyl,(R₄)3N-alkyl, (R₄)₃N-2-hydroxyalkyl, C₆-C₁₂ aryloxy-2-hydroxyalkyl,

each R₄ is independently selected from the group consisting of H, C₁-C₂₀alkyl, C₅-C₇ cycloalkyl, C₇-C₂₀ alkylaryl, C₇-C₂₀ arylalkyl, aminoalkyl,alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl,cycloalkylaminoalkyl and hydroxyalkyl;

each R₅ is independently selected from the group consisting of H, C₁-C₂₀alkyl, C₅-C₇ cycloalkyl, C₇-C₂₀ alkylaryl, C₇-C₂₀ arylalkyl, substitutedalkyl, hydroxyalkyl, (R₄)₂N-alkyl, and (R₄)₃N-alkyl;

wherein:

M is a suitable cation selected from the group consisting of Na, K,1/2Ca, and 1/2Mg;

each x is from 0 to about 5;

each y is from about 1 to about 5; and

provided that:

the Degree of Substitution for group R_(H) is between about 0.001 and0.1, more preferably between about 0.005 and 0.05, and most preferablybetween about 0.01 and 0.05;

the Degree of Substitution for group R_(C) wherein Z is H or M isbetween about 0.2 and 2.0, more preferably between about 0.3 and 1.0,and most preferably between about 0.4 and 0.7;

if any R_(H) bears a positive charge, it is balanced by a suitableanion; and

two R₄'s on the same nitrogen can together form a ring structureselected from the group consisting of piperidine and morpholine.

The “Degree of Substitution” for group R_(H), which is sometimesabbreviated herein “DS_(RH)”, means the number of moles of group R_(H)components that are substituted per anhydrous glucose unit, wherein ananhydrous glucose unit is a six membered ring as shown in the repeatingunit of the general structure above.

The “Degree of Substitution” for group R_(C), which is sometimesabbreviated herein “DS_(RC)”, means the number of moles of group R_(C)components, wherein Z is H or M, that are substituted per anhydrousglucose unit, wherein an anhydrous glucose unit is a six membered ringas shown in the repeating unit of the general structure above. Therequirement that Z be H or M is necessary to insure that there are asufficient number of carboxy methyl groups such that the resultingpolymer is soluble. It is understood that in addition to the requirednumber of R_(C) components wherein Z is H or M, there can be, and mostpreferably are, additional R_(C) components wherein Z is a group otherthan H or M.

These polymers can for example be obtained by use of processes asdescribed in co-pending application PCT/US98/19139 and PCT/US98/19142.

Quaternary Ammonium Compounds

The compositions or components of the invention comprise a quaternaryammonium compound. This compound is preferably selected from quaternaryammonium surfactants, quaternary ammonium softeners, quaternary ammoniumdispersants, described herein after. Highly preferred are the quatemaryammonium surfactants.

The levels of the quaternary ammonium surfactants used in detergentcompositions of the invention are preferably from 0.1% to 20%,preferably from 0.4% to 7%, most preferably from 0.5% to about 5.0%, byweight of the detergent composition. The levels of the quaternaryammonium surfactants in components or additives of the invention arepreferably from 0.1% to 90%, preferably from 0.5% to 50%, mostpreferably from 2% to about 30%, by weight of the detergent component oradditive.

The levels of the quaternary ammonium softeners used in detergentcompositions of the invention are preferably from 0.1% to 20%,preferably from 0.4% to 15%, most preferably from 0.5% to about 10%, byweight of the detergent composition. The levels of the quaternaryammonium surfactants in components or additive of the invention arepreferably from 0.1% to 90%, preferably from 0.5% to 50%, mostpreferably from 2% to about 30%, by weight of the detergent component oradditive.

The levels of the quaternary ammonium dispersant used in detergentcompositions of the invention are preferably from 0.05% to 10%,preferably from 0.1% to 7%, most preferably from 0.5% to about 5.0%, byweight of the detergent composition. The levels of the quatemaryammonium surfactants in components or additive of the invention arepreferably from 0.1% to 60%, preferably from 0.5% to 40%, mostpreferably from 0.5% to about 25%, by weight of the detergent componentor additive.

Ouaternary Ammonium Surfactants

Preferably, the cationic surfactant herein is selected from the groupconsisting of cationic mono-alkoxylated amine surfactants (not being thesodium salt of the cationic C₁₂-C₁₄ alkyl dimethyl ammonium ethanolsurfactant), cationic bis-alkoxylated amine surfactants and mixturesthereof. Also preferred are salts of the cationic C₁₂-C₁₄ alkyl dimethylammonium ethanol surfactant.

Cationic Mono-alkoxylated Amine Surfactants

The cationic surfactant herein can be a cationic mono-alkoxylated aminesurfactant, which has the general formula I:

wherein R¹ is an alkyl or alkenyl moiety containing from about 6 toabout 18 carbon atoms, preferably 6 to about 16 carbon atoms, mostpreferably from about 6 to about 14 carbon atoms; R² and R³ are eachindependently alkyl groups containing from one to about three carbonatoms, preferably methyl, most preferably both R² and R³ are methylgroups; R⁴ is selected from hydrogen (preferred), methyl and ethyl; X⁻is an anion such as chloride, bromide, methylsulfate, sulfate, or thelike, to provide electrical neutrality; A is a alkoxy group, especiallya ethoxy, propoxy or butoxy group; and p is from 0 to about 30,preferably 2 to about 15, most preferably 2 to about 8.

Preferably the ApR⁴ group in formula I has p=1 and is a hydroxyalkylgroup, having no greater than 6 carbon atoms whereby the —OH group isseparated from the quaternary ammonium nitrogen atom by no more than 3carbon atoms. Particularly preferred ApR⁴ groups are —CH₂CH₂OH,—CH₂CH₂CH₂OH, —CH₂CH(CH₃)OH and —CH(CH₃)CH₂OH, with —CH₂CH₂OH beingparticularly preferred. Preferred R¹ groups are linear alkyl groups.Linear R¹ groups having from 8 to 22 carbon atoms, or from 9 to 16carbon atoms are preferred. Such a cationic surfactant which is highlypreferred has a formula wherein R¹ is a C₈-C₁₀ or a C₁₂-C₁₄ alkyl group,p is 1, A is ethoxy and R₂ and R₃ are methyl groups.

It has been found that mixtures of the cationic surfactants of formula Imay be particularly effective, for example, surfactant mixtures in whichR¹ may be a combination of C₈ and C₁₀ linear alkyl groups, C₉ and C₁₁alkyl groups, C₁₂ and C₁₄ alkyl groups.

Another highly preferred cationic mono-alkoxylated amine surfactants foruse herein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, especiallyC₁₀-C₁₄ alkyl, preferably C₁₀ and C₁₂ alkyl, and X is any convenientanion to provide charge balance, preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein theethoxy (CH₂CH₂O) units (EO) are replaced by butoxy, isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

When used in granular detergent compositions cationic mono-alkoxylatedamine surfactants wherein the hydrocarbyl substituent R¹ is C₈-C₁₄ canbe preferred, because they enhance the rate of dissolution of laundrygranules, especially under cold water conditions, as compared with thehigher chain length materials.

Cationic Bis-alkoxvlated Amine Surfactant

The cationic surfactant herein can be a cationic bis-alkoxylated aminesurfactant, which has the general formula II:

wherein R¹ is an alkyl or alkenyl moiety containing from about 8 toabout 18 carbon atoms, preferably 10 to about 16 carbon atoms, mostpreferably from about 10 to about 14 carbon atoms; R₂ is an alkyl groupcontaining from one to three carbon atoms, preferably methyl; R³ and R⁴can vary independently and are selected from hydrogen (preferred),methyl and ethyl, X⁻ is an anion such as chloride, bromide,methylsulfate, sulfate, or the like, sufficient to provide electricalneutrality. A and A′ can vary independently and are at each selectedfrom C₁-C₄ alkoxy, especially ethoxy, (i.e., —CH₂CH₂O—), propoxy, butoxyand mixtures thereof; p is from 1 to about 30, preferably 1 to about 4and q is from 1 to about 30, preferably 1 to about 4, and mostpreferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for useherein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, preferably C₁₀,C₁₂, C₁₄ alkyl and mixtures thereof. X is any convenient anion toprovide charge balance, preferably chloride. With reference to thegeneral cationic bis-alkoxylated amine structure noted above, since in apreferred compound R¹ is derived from (coconut) C₁₂-C₁₄ alkyl fractionfatty acids, R² is methyl and ApR³ and A′qR⁴ are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein includecompounds of the formula:

wherein R¹ is C₁₀-C₁₈ hydrocarbyl, preferably C₁₀-C₁₄ alkyl,independently p is 1 to about 3 and q is 1 to about 3, R² is C₁-C₃alkyl, preferably methyl, and X is an anion, especially chloride orbromide.

Other compounds of the foregoing type include those wherein the ethoxy(CH₂CH₂O) units (EO) are replaced by butoxy (Bu) isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

When used in granular detergent compositions in accord with theinvention, cationic bis alkoxylated amine surfactants wherein thehydrocarbyl substituent R¹ is C₈-C₁₄, can be preferred cationicsurfactants, because they enhance the rate of dissolution of laundrygranules, especially under cold water conditions, as compared with thehigher chain length materials.

A cationic surfactant according to the present invention comprises atleast one quatemized ammonium group and at least one primary, secondaryor tertiary amine group, whereby not more than one linear or branchedpolyoxyalkylene group is present as substituent group.

OUATERNARY POLYAMINE SURFACTANT

Examples of preferred qaternary polyamine surfactants for use hereinare:

wherein R₁, R₄, R₆ and R₈ are as described above; R₂, R₃ and R₅ areindependently selected from the group consisting of methyl, ethyl,hydroxyethyl, hydroxypropyl, polyhydroxy propyl, ethoxy, propoxy or2,3,4,5,6-penta hydroxy hexyl, and are most preferably methyl orhydroxyethyl groups; R₁₀ is a methyl or hydroxyethyl group; L is asdescribed above; R₁ and/or R₂ and/or R₄ are most preferably a2-ethylhexyl group.

A highly preferred cationic polyamine surfactant is of formula VI, asdefined above, wherein R₂ is a hydroxypropyl or hydroxyethyl group, R₃and R₁₀ are methyl groups, L is C₂-C₃ alkyl group.

Highly preferred polyamine cationic surfactant are those of theformulas:

or

wherein R₁ is as described above, preferably a C₂-C₁₄, preferably C₆-C₁₄linear or branched alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group;particularly preferred R₁ groups are hydroxyalkyl groups, where thealkyl groups have 2 to 5 carbon atoms, especially hydroxyethyl andhydroxypropyl are preferred; particularly preferred alkyl R₁ groups haveup to 9 carbon atoms, most preferably R₁ is a 2-ethylhexyl group; andR₁₁ is a C₂-C₁₄ alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group.

The anion M⁻ is a counterion for the cationically charged polyaminesurfactant, preferably bromide or more preferably chloride.

Ouaternary Ammonium Dispersant

The dispersant for use herein can be any of the compounds as describedin EP-B-011965 and U.S. Pat. No. 4,659,802 and U.S. Pat. No. 4,664,848.

Preferred quaternary ammonium dispersants are monoamines and diamines ofthe formula:

wherein X is a nonionic group selected from the group consisting of H,C₁-C₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof,a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene,hexamethylene), b is 1 or 0; for cationic monoamines (b=0), n is atleast 16, with a typical range of from 20 to 35; highly preferred arediamines (b=1), whereby n is at least about 12 with a typical range offrom about 12 to about 42, and a is preferably 4.

Ouaternary Softener Compounds

The quaternary softener compounds herein are preferably quatemaryammonium compounds having one or two C12-C24 alkyl or alkenyl chains,optionally substituted with one or more functional groups such as —OH,—O—, CONH, —COO—, and with two or three C1-C11, preferably C-C6 or evenC1 to C4 alkyl or alkenyl groups, optionally substituted with afunctional groups such as —OH, —O—, CONH, —COO— or mixtures thereof.

Preferably, they are di-long-chain amides as disclosed in EP-B-0 242919.Preferably, when comprising two C12-C24 groups, they comprise two C1-C4groups, preferably methyl or ethyl groups.

When the softeners comprise three C1-C11 alkyl or alkenyl groups, theypreferably comprise an C18-C24 alkyl or akenyl group.

The anion is preferably chloride or bromide.

Other preferred cationic softeners are for example described in U.S.Pat. No. 5,540,850.

Detergent Compositions or Components

The compositions or components of the invention are preferably laundry,compositions, preferably in the form of granules, extrudates, flakes ortablets, liquids or pastes.

The compositions or components in accord with the invention may alsocontain additional detergent components. The precise nature of theseadditional components, and levels of incorporation thereof will dependon the physical form of the composition or component, and the precisenature of the washing operation for which it is to be used.

They preferably contain one or more additional detergent componentsselected from surfactants, bleaches, bleach catalysts, alkalinitysystems, builders, phosphate-containing builders, organic polymericcompounds, enzymes, suds suppressors, lime soap, dispersants, soilsuspension and anti-redeposition agents soil releasing agents, perfumes,brightners, photobleaching agents and additional corrosion inhibitors.

Preferred additional ingredients are cyclic amine based polymers asdescribed in co-pending application PCT/US98/19143 and PCT/US98/19141,in particular those compounds described therein in the examples, inparticular example 1 and 2. These polymers may be present at a level offrom 0.01% to 10% by weight of the composition, more preferably at alevel of from 0.05% to 5% by weight or even form 0.1% to 2% by weight ofthe composition, or at a level of from 0.05% to 30% by weight of thecomponent, more preferably at a level of from 0.1% to 20% by weight oreven form 0.3% to 10% by weight of the component.

Surfactant

The components or compositions in accord with the invention preferablycontain one or more surfactants selected from anionic, nonionic,cationic, ampholytic, amphoteric and zwittenronic surfactants andmixtures thereof.

A typical listing of anionic, nonionic, ampholytic, and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,929,678 issued to Laughlin and Heurinrg on Dec. 30, 1975. Furtherexamples are given in “Surface Active Agents and Detergents” (Vol. I andII by Schwartz, Perry and Berch). A list of suitable cationicsurfactants is given in U.S. Pat. No. 4,259,217 issued to Murphy on Mar.31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants aregenerally used in combination with one or more anionic and/or nonionicsurfactants.

Anionic Surfactant

The components or compositions in accord with the present inventionpreferably comprise an additional anionic surfactant. Essentially anyanionic surfactants useful for detersive purposes can be comprised inthe detergent components or compositions. These can include salts(including, for example, sodium, potassium, ammonium, and substitutedammonium salts such as mono-, di- and triethanolamine salts) of theanionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.Anionic sulfate and sulfonate surfactants are preferred.

Highly preferred are surfactants systems comprising a sulfonate and asulfate surfactant, preferably a linear or branched alkyl benzenesulfonate and alkyl ethoxylsulfates, as described herein, preferablycombined with a cationic surfactants as described herein.

Other anionic surfactants include the isethionates such as the acylisethionates, N-acyl taurates, fatty acid amides of methyl tauride,alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆-C₁₄ diesters),N-acyl sarcosinates. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.

Anionic Sulfate Surfactant

Anionic sulfate surfactants suitable for use herein include the linearand branched primary and secondary alkyl sulfates, alkyl ethoxysulfates,fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ethersulfates, the C₅-C₁₇ acyl-N-(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl)glucamine sulfates; and sulfates of alkylpolysaccharides such as thesulfates of alkylpolyglucoside (the nonionic nonsulfated compounds beingdescribed herein).

Alkyl sulfate surfactants are preferably selected from the linear andbranched primary C₁₀-C₁₈ alkyl sulfates, more preferably the C₁₁—C₁₅branched chain alkyl sulfates and the C₁₂-C₁₄ linear chain alkylsulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the groupconsisting of the C₁₀-C₁₈ alkyl sulfates which have been ethoxylatedwith from 0.5 to 20 moles of ethylene oxide per molecule. Morepreferably, the alkyl ethoxysulfate surfactant is a C₁₁-C₁₈, mostpreferably C₁₁-C₁₅ alkyl sulfate which has been ethoxylated with from0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of thepreferred alkyl sulfate and/or sulfonate and alkyl ethoxysulfatesurfactants. Such mixtures have been disclosed in PCT Patent ApplicationNo. WO 93/18124.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use herein include the saltsof C₅-C₂₀ linear alklylbenzene sulfonates, alkyl ester sulfonates,C₆-C₂₂ primary or secondary alkane sulfonates, C₆-C₂₄ olefin sulfonates,sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixturesthereof.

Anionic Carboxylate Surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxy polycarboxylate surfactants and thesoaps (‘alkyl carboxyls’), especially certain secondary soaps asdescribed herein.

Suitable alkyl ethoxy carboxylates include those with the formulaRO(CH₂CH₂O)_(x) CH₂COO⁻M⁺ wherein R is a C₆ to C₁₈ alkyl group, x rangesfrom 0 to 10, and the ethoxylate distribution is such that, on a weightbasis, the amount of material where x is 0 is less than 20% and M is acation. Suitable alkyl polyethoxy polycarboxylate surfactants includethose having the formula RO—(CHR₁—CHR₂—O)—R₃ wherein R is a C₆ to C₁₈alkyl group, x is from 1 to 25, R₁ and R₂ are selected from the groupconsisting of hydrogen, methyl acid radical, succinic acid radical,hydroxysuccinic acid radical, and mixtures thereof, and R₃ is selectedfrom the group consisting of hydrogen, substituted or unsubstitutedhydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof

Suitable soap surfactants include the secondary soap surfactants whichcontain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoicacid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Certain soaps may also be included as suds suppressers.

Alkali Metal Sarcosinate Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates offormula R—CON (R₁) CH₂ COOM, wherein R is a C₅-C₁₇ linear or branchedalkyl or alkenyl group, R₁ is a C₁-C₄ alkyl group and M is an alkalimetal ion. Preferred examples are the myristyl and oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated Nonionic Surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein.The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes ofthe nonionic condensates of alkyl phenols, nonionic ethoxylatedalcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionicethoxylate/propoxylate condensates with propylene glycol, and thenonionic ethoxylate condensation products with propylene oxide/ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactant

The condensation products of aliphatic alcohols with from 1 to 25 molesof alkylene oxide, particularly ethylene oxide and/or propylene oxide,are suitable for use herein. The alkyl chain of the aliphatic alcoholcan either be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms. Particularly preferred are thecondensation products of alcohols having an alkyl group containing from8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per moleof alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those havingthe structural formula R²CONR¹Z wherein: R1 is H, C₁-C₄ hydrocarbyl,2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixturethereof, preferable C1-C4 alkyl, more preferably C₁ or C₂ alkyl, mostpreferably C₁ alkyl (i.e., methyl); and R₂ is a C₅-C₃₁ hydrocarbyl,preferably straight-chain C₅-C₁₉ alkyl or alkenyl, more preferablystraight-chain C₉-C₁₇ alkyl or alkenyl, most preferably straight-chainC₁₁-C₁₇ alkyl or alkenyl, or mixture thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction;.morepreferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those having the formula:R⁶CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7 to 21,preferably from 9 to 17 carbon atoms and each R⁷ is selected from thegroup consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, and—(C₂H₄O)_(x)H, where x is in the range of from 1 to 3.

Nonionic Alkylpolysaccharide Surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from 6 to 30 carbon atoms and a polysaccharide, e.g., apolyglycoside, hydrophilic group containing from 1.3 to 10 saccharideunits.

Preferred alkylpolyglycosides have the formula:

R²O(C_(n)H_(2n)O)t(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived fromglucose.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formulaR³(OR⁴)_(x)N⁰(R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containingfrom 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene groupcontaining from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl groupcontaining from 1 to 3, or a polyethylene oxide group containing from 1to 3 ethylene oxide groups. Preferred are C₁₀-C₁₈ alkyl dimethylamineoxide, and C₁₀₋₁₈ acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, N.J.

Zwitterionic Surfactant

Zwitterionic surfactants can also be incorporated into the detergentcomponents or compositionss in accord with the invention. Thesesurfactants can be broadly described as derivatives of secondary andtertiary amines, derivatives of heterocyclic secondary and tertiaryamines, or derivatives of quaternary ammonium, quaternary phosphonium ortertiary sulfonium compounds. Betaine and sultaine surfactants areexemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R′)₂N⁺R²COO—wherein R is a C₆-C₁₈ hydrocarbyl group, each R¹ is typically C₁-C₃alkyl, and R² is a C₁-C₅ hydrocarbyl group. Preferred betaines areC₁₂₋₁₈ dimethyl-ammonio hexanoate and the C₁₀₋₁₈ acylamidopropane (orethane) dimethyl (or diethyl) betaines. Complex betaine surfactants arealso suitable for use herein.

Perhydrate Bleaches

An preferred additional components of the components or compositions isa perhydrate bleach, such as metal perborates, metal percarbonates,particularly the sodium salts. Perborate can be mono or tetra hydrated.Sodium percarbonate has the formula corresponding to 2Na₂CO₃.3H₂O₂, andis available commercially as a crystalline solid.

Potassium peroxymonopersulfate, sodium per is another optional inorganicperhydrate salt of use in the detergent components or compositionsherein.

Organic Peroxyacid Bleaching System

A preferred feature of the components or compositions is an organicperoxyacid bleaching system. In one preferred execution the bleachingsystem contains a hydrogen peroxide source and an organic peroxyacidbleach precursor compound. The production of the organic peroxyacidoccurs by an in situ reaction of the precursor with a source of hydrogenperoxide. Preferred sources of hydrogen peroxide include inorganicperhydrate bleaches, such as the perborate bleach of the claimedinvention. In an alternative preferred execution a preformed organicperoxyacid is incorporated directly into the components or compositions.Components or compositions containing mixtures of a hydrogen peroxidesource and organic peroxyacid precursor in combination with a preformedorganic peroxyacid are also envisaged.

Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogenperoxide in a perhydrolysis reaction to produce a peroxyacid. Generallyperoxyacid bleach precursors may be represented as

where L is a leaving group and X is essentially any functionality, suchthat on perhydroloysis the structure of the peroxyacid produced is

Peroxyacid bleach precursor compounds are preferably incorporated at alevel of from 0.5% to 20% by weight, more preferably from 1% to 15% byweight, most preferably from 1.5% to 10% by weight of the detergentcompositions.

Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a widerange of classes. Suitable classes include anhydrides, esters, imides,lactams and acylated derivatives of imidazoles and oximes. Examples ofuseful materials within these classes are disclosed in GB-A-1586789.Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231and EP-A-0170386.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactivefor the perhydrolysis reaction to occur within the optimum time frame(e.g., a wash cycle). However, if L is too reactive, this activator willbe difficult to stabilize for use in a bleaching components orcompositions.

Preferred L groups are selected from the group consisting of:

and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl groupcontaining from 1 to 14 carbon atoms, R³ is an alkyl chain containingfrom 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizinggroup. Any of R¹, R³ and R⁴ may be substituted by essentially anyfunctional group including, for example alkyl, hydroxy, alkoxy, halogen,amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are —SO₃ ³¹ M⁺, —CO₂ ⁻M⁺, —SO₄ ⁻M⁺,—N⁺(R³)₄X⁻ and O←N(R³)₃ and most preferably —SO₃ ⁻M⁺ and —CO₂ ⁻M⁺wherein R³ is an alkyl chain containing from 1 to 4 carbon atoms, M is acation which provides solubility to the bleach activator and X is ananion which provides solubility to the bleach activator. Preferably, Mis an alkali metal, ammonium or substituted ammonium cation, with sodiumand potassium being most preferred, and X is a halide, hydroxide,methylsulfate or acetate anion.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acidon perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide typeinclude the N-,N,N¹N¹ tetra acetylated alkylene diamines wherein thealkylerie group contains from 1 to 6 carbon atoms, particularly thosecompounds in which the alkylene group contains 1, 2 and 6 carbon atoms.Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodiumnonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate(ABS) and pentaacetyl glucose.

Amide Substituted Alkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitableherein, including those of the following general formulae:

wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is analkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or analkyl group containing 1 to 10 carbon atoms and L can be essentially anyleaving group. Amide substituted bleach activator compounds of this typeare described in EP-A-0170386.

Preformed Organic Peroxyacid

The detergent composition may contain, in addition to, or as analternative to, an organic peroxyacid bleach precursor compound, apreformed organic peroxyacid, typically at a level of from 1% to 15% byweight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amidesubstituted compounds of the following general formulae:

wherein R¹ is an alkyl, aryl or alkaryl group with from 1 to 14 carbonatoms, R² is an alkylene, arylene, and alkarylene group containing from1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl groupcontaining 1 to 10 carbon atoms. Amide substituted organic peroxyacidcompounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides,especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid anddiperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- anddiperbrassylic acid and N-phthaloylaminoperoxicaproic acid are alsosuitable herein.

Water-Soluble Builder Compound

The components or compositions in accord with the present inventionpreferably contain a water-soluble builder compound, typically presentin detergent compositions at a level of from 1% to 80% by weight,preferably from 10% to 60% by weight, most preferably from 15% to 40% byweight of the composition.

The detergent components or compositions of the invention preferablycomprise phosphate-containing builder material. Preferably present at alevel of from 0.5% to 60%, more preferably from 5% to 50%, morepreferably from 8% to 40.

The phosphate-containing builder material preferably comprisestetrasodium pyrophosphate or even more preferably anhydrous sodiumtripolyphosphate.

Suitable water-soluble builder compounds include the water solublemonomeric polycarboxylates, or their acid forms, homo or copolymericpolycarboxylic acidsor their salts in which the polycarboxylic acidcomprises at least two carboxylic radicals separated from each other bynot more that two carbon atoms, borates, and mixtures of any of theforegoing.

The carboxylate or polycarboxylate builder can be momomeric oroligomeric in type although monomeric polycarboxylates are generallypreferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivativesthereof. Polycarboxylates containing two carboxy groups include thewater-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronicacid and fumaric acid, as well as the ether carboxylates and thesulfinyl carboxylates. Polycarboxylates or their acids containing threecarboxy groups include, in particular, water-soluble citrates,aconitrates and citraconates as well as succinate derivatives such asthe carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in British Patent No. 1,389,732,and aminosuccinates described in Netherlands Application 7205873, andthe oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylates described in British Patent No. 1,387,447. The mostpreferred polycarboxylic acid containing three carboxy groups is citricacid, preferably present at a level of from 0.1% to 15%, more preferablyfrom 0.5% to 8% by weight of the composition.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,439,000.Preferred polycarboxylates are hydroxycarboxylates containing up tothree carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylatechelating agents or mixtures thereof with their salts, e.g. citric acidor citrate/citric acid mixtures are also contemplated as useful buildercomponents.

Borate builders, as well as builders containing borate-forming materialsthat can produce borate under detergent storage or wash conditions areuseful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkalimetal tripolyphosphates, sodium, potassium and ammonium pyrophosphate,sodium and potassium and ammonium pyrophosphate, sodium and potassiumorthophosphate, sodium polymeta/phosphate in which the degree ofpolymerization ranges from about 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compound

The components or compositions in accord with the present invention maycontain a partially soluble or insoluble builder compound, typicallypresent in detergent compositions at a level of from 0.5% to 60% byweight, preferably from 5% to 50% by weight, most preferably from 8% to40% weight of the composition.

Examples of largely water insoluble builders include the sodiumaluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formulaNa_(z)[(AlO₂)_(z)(SiO₂)y]. xH₂O wherein z and y are at least 6; themolar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferablyfrom 7.5 to 276, more preferably from 10 to 264. The aluminosilicatematerial are in hydrated form and are preferably crystalline, containingfrom 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, butare preferably synthetically derived. Synthetic crystallinealuminosilicate ion exchange materials are available under thedesignations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS andmixtures thereof. Zeolite A has the formula:

Na₁₂[AlO₂)₁₂(SiO₂)₁₂]. xH₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formulaNa₈₆ [(AlO₂)₈₆(SiO₂)₁₀₆]. 276 H₂O.

Another preferred aluminosilicate zeolite is zeolite MAP builder. Thezeolite MAP can be present at a level of from 1% to 80%, more preferablyfrom 15% to 40% by weight of the compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as analkali metal alumino-silicate of the zeolite P type having a silicon toaluminum ratio not greater than 1.33, preferably within the range from0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminum rationot greater than 1.15 and, more particularly, not greater than 1.07.

In a preferred aspect the zeolite MAP detergent builder has a particlesize, expressed as a d₅₀ value of from 1.0 to 10.0 micrometres, morepreferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0micrometres.

The d₅₀ value indicates that 50% by weight of the particles have adiameter smaller than that figure. The particle size may, in particularbe determined by conventional analytical techniques such as microscopicdetermination using a scanning electron microscope or bymeans of a lasergranulometer. Other methods of establishing d₅₀ values are disclosed inEP 384070A.

Heavy Metal Ion Sequestrant

The components or compositions of the invention preferably contain as anoptional component a heavy metal ion sequestrant. By heavy metal ionsequestrant it is meant herein components which act to sequester(chelate) heavy metal ions. These components may also have calcium andmagnesium chelation capacity, but preferentially they show selectivityto binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to7.5% and most preferably from 0.3% to 2% by weight of the compositionsor component

Suitable heavy metal ion sequestrants for use herein include organicphosphonates, such as the amino alkylene poly (alkylene phosphonates),alkali metal ethane 1-hydrbxy disphosphonates andnitrilo trimethylenephosphonates.

Preferred among the above species are diethylene triamine penta(methylene phosphonate), ethylene diamine tri (methylene phosphonate)hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1hydroxyethane dimethylene phosphonic acid.

Other suitable heavy metal ion sequestrant for use herein includenitrilotriacetic acid and polyaminocarboxylic acids such asethylenediaminotetracetic acid, ethylenediamine disuccinic acid,ethylenediamine diglutaric acid, 2-hydroxypropylenediarnine disuccinicacid or any salts thereof.

Other suitable heavy metal ion sequestrants for use herein areiminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid orglyceryl imino diacetic acid, described in EP-A-317,542 andEP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid andaspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acidsequestrants described in EP-A-516,102 are also suitable herein. Theβ-alanine-N,N′-diacetic acid, aspartic acid-N,N′-diacetic acid, asparticacid-N-monoacetic acid and iminodisuccinic acid sequestrants describedin EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331describes suitable sequestrants derived from collagen, keratin orcasein. EP-A-528,859 describes a suitable alkyl iminodiacetic acidsequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylicacid are also suitable. Glycinamide-N,N′-disuccinic acid (GADS),ethylenediamine-N-N′-diglutaric acid (EDDG) and2-hydroxypropylenediamine-N-N′-disuccinic acid (HPDDS) are alsosuitable.

Especially preferred are diethylenetriamine pentacetic acid,ethylenediamine-N,N′-disuccinic acid (EDDS) and 1,1 hydroxyethanediphosphonic acid or the alkali metal, alkaline earth metal, ammonium,or substituted ammonium salts thereof, or mixtures thereof.

Enzyme

Another preferred ingredient useful in the components or compositionsherein is one or more additional enzymes.

Preferred additional enzymatic materials include the commerciallyavailable lipases, cutinases, amylases, neutral and alkaline proteases,cellulases, endolases, esterases, pectinases, lactases and peroxidasesconventionally incorporated into detergent components or compositionss.Suitable enzymes are discussed in U.S. Pat. Nos. 3,519,570 and3,533,139.

Preferred commercially available protease enzymes include those soldunder the tradenames Alcalase, Savinase, Primase, Durazym, and Esperaseby Novo Industries A/S (Denmark), those sold under the-tradenameMaxatase, Maxacal and Maxapem by Gist-Brocades, those sold by GenencorInternational, and those sold under the tradename Opticlean and Optimaseby Solvay Enzymes. Protease enzyme may be incorporated into thecompositions in accordance with the invention at a level of from 0.0001%to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, c-amylases obtained from aspecial strain of B licheniformis, described in more detail inGB-1,269,839 (Novo). Preferred commercially available amylases includefor example, those sold under the tradename Rapidase by Gist-Brocades,and those sold under the tradename Termamyl, Duramyl and BAN by NovoIndustries A/S. Highly preferred amylase enzymes-maybe those describedin PCT/US 9703635, and in WO95/26397 and WO96/23873.

Amylase enzyme may be incorporated into the composition in accordancewith the invention at a level of from 0.0001% to 2% active enzyme byweight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme offrom 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, mostpreferably from 0.001% to 0.5% by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, forexample, from a lipase producing strain of Humicola sp., Thermomyces sp.or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomasfluorescens. Lipase from chemically or genetically modified mutants ofthese strains are also useful herein. A preferred lipase is derived fromPseudomonas pseudoalcaligenes, which is described in Granted EuropeanPatent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene fromHumicola lanuginosa and expressing the gene in Asperpillus orvza, ashost, as described in European Patent Application, EP-A-0258 068, whichis commercially available from Novo Industri A/S, Bagsvaerd, Denmark,under the trade name Lipolase. This lipase is also described in U.S.Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components of thecomponents or compositions herein and are preferably present ascomponents of any particulate components where they may act such as tobind the particulate component together. By organic polymeric compoundit is meant herein essentially any polymeric organic compound commonlyused as dispersants, and anti-redeposition and soil suspension agents indetergent components or compositionss, including any of the highmolecular weight organic polymeric compounds described as clayflocculating agents herein, including quaternised ethoxylated (poly)amine clay-soil removal anti-redeposition agent in accord with theinvention.

Organic polymeric compound is typically incorporated in the detergentcompositions of the invention at a level of from 0.01% to 30%,preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weightof the compositions.

Examples of organic polymeric compounds include the water solubleorganic homo- or co-polymeric polycarboxylic acids or their salts inwhich the polycarboxylic acid comprises at least two carboxyl radicalsseparated from each other by not more than two carbon atoms. Polymers ofthe latter type are disclosed in GB-A-1,596,756. Examples of such saltsare polyacrylates of MWt 1000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 2000 to100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived fromaspartic acid such as those disclosed in EP-A-305282, EP-A-305283 andEP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylicacid, polyaspartic acid and vinyl alcohol, particularly those having anaverage molecular weight of from 5,000 to 10,000, are also suitableherein.

Other organic polymeric compounds suitable for incorporation in thedetergent components or compositionss herein include cellulosederivatives such as methylcellulose, carboxymethylcellulose,hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000.

Highly preferred polymeric components herein are cotton and non-cottonsoil release polymer according to U.S. Pat. No. 4,968,451, Scheibel etal., and U.S. Pat. No. 5,415,807, Gosselink et al., and in particularaccording to U.S. application Ser. No. 60/051517.

Suds Suppressing System

The detergent compositions of the invention, when, formulated for use inmachine washing compositions, may comprise a suds suppressing systempresent at a level of from 0.01% to 15%, preferably from 0.02% to 10%,most preferably from 0.05% to 3% by weight of the composition.

Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for example siliconeantifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures ofcompounds which act such as to depress the foaming or sudsing producedby a solution of a detergent composition, particularly in the presenceof agitation of that solution.

Particularly preferred antifoam compounds for use herein are siliconeantifoam compounds defined herein as any antifoam compound including asilicone component. Such silicone antifoam compounds also typicallycontain a silica component. The term “silicone” as used herein, and ingeneral throughout the industry, encompasses a variety of relativelyhigh molecular weight polymers containing siloxane units and hydrocarbylgroup of various types. Preferred silicone antifoam compounds are thesiloxanes, particularly the polydimethylsiloxanes having trimethylsilylend blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acidsand soluble salts thereof. These materials are described in U.S. Pat.No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Themonocarboxylic fatty acids, and salts thereof, for use as sudssuppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,preferably 12 to 18 carbon atoms. Suitable salts include the alkalimetal salts such as sodium, potassium, and lithium salts, and ammoniumand alkanolammonium salts.

Other suitable anti foam compounds include, for example, high molecularweight fatty esters (e.g. fatty acid triglycerides), fatty acid estersof monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g. stearone)N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amideand monostearyl di-alkali metal (e.g. sodium, potassium, lithium)phosphates and phosphate esters.

A preferred suds suppressing system comprises:

(a) antifoam compound, preferably silicone antifoam compound, mostpreferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75%to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% byweight of the silicone/silica antifoam compound;

 wherein said silica/silicone antifoam compound is incorporated at alevel of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycolrake copolymer with a polyoxyalkylene content of 72-78% and an ethyleneoxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level offrom 0.5% to 10%, preferably 1% to 10% by weight; a particularlypreferred silicone glycol rake copolymer of this type is DCO544,commercially available from DOW Coming under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising aC₁₆-C₁₈ ethoxylated alcohol with a degree of ethoxylation of from 5 to50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to70%, by weight;

A highly preferred particulate suds suppressing system is described inEP-A-0210731 and comprises a silicone antifoam compound and an organiccarrier material having a melting point in the range 50° C. to 85° C.,wherein the organic carrier material comprises a monoester of glyceroland a fatty acid having a carbon chain containing from 12 to 20 carbonatoms. EP-A-0210721 discloses other preferred particulate sudssuppressing systems wherein the organic carrier material is a fatty acidor alcohol having a carbon chain containing from 12 to 20 carbon atoms,or a mixture thereof, with a melting point of from 45° C. to 80° C.

Other highly preferred suds suppressing systems comprisepolydimethylsiloxane or mixtures of silicone, such aspolydimethylsiloxane, aluminosilicate and polycarboxylic polymers, suchas copolymers of laic and acrylic acid.

Polymeric Dye Transfer Inhibiting Apents

The compositions herein may also comprise from 0.01% to 10%, preferablyfrom 0.05% to 0.5% by weight of polymeric dye transfer inhibitingagents.

The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof,whereby these polymers can be cross-linked polymers.

Optical Brightener

The compositions herein also optionally contain from about 0.005% to 5%by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having thestructural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂, is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4′-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferredhydrophilic optical brightener useful in the detergent compositionsherein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino)]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species are commerciallymarketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by CibaGeigy Corporation.

Polymeric Soil Release Agent

Additional polymeric soil release agents, hereinafter “SRA”, canoptionally be employed in the present compositions. If utilized, SRA'swill generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%,preferably from 0.2% to 3.0% by weight, of the compositions.

The additional SRP's include hydrophivally modified cellulosederivatives, such as ester derivatives of CMC. Also included arenonionic cellulose ethers and derivatives.

Preferred SRA's typically have hydrophilic segments to hydrophilize thesurface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles,thereby serving as an anchor for the hydrophilic segments. This canenable stains occurring subsequent to treatment with the SRA to be moreeasily cleaned in later washing procedures.

Preferred SRA's include oligomeric terephthalate esters, typicallyprepared by processes involving at least onetransesterification/oligomerization, often with a metal catalyst such asa titanium(IV) alkoxide. Such esters may be made using additionalmonomers capable of being incorporated into the ester structure throughone, two, three, four or more positions, without, of course, forming adensely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linearester oligomer comprised of an oligoimeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl-derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990 to J. J.Scheibel and E. P. Gosselink. Such ester oligomers can be prepared by:(a) ethoxylating allyl alcohol; (b) reacting the product of (a) withdimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in atwo-stage transesterification/oligomerization procedure; and (c)reacting the product of (b) with sodium metabisulfite in water. OtherSRA's include the nonionic end-capped 1,2-propylene/polyoxyethyleneterephthalate polyesters of U.S. Pat. No. 4,711,730, Dec. 8, 1987 toGosselink et al., for example those produced bytransesterification/oligomerization of poly(ethyleneglycol) methylether, DMT, PG and poly(ethyleneglycol) (“PEG”). Other examples of SRA'sinclude: the partly- and fully-anionic-end-capped oligomeric esters ofU.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomersfrom ethylene glycol (“EG”), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, methyl (Me)-capped PEG andEG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31,1989 to Maldonado, Gosselink et al., the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an examplebeing an ester composition made from m-sulfobenzoic acid monosodiumsalt, PG and DMT, optionally but preferably further comprising addedPEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalateor propylene terephthalate with polyethylene oxide or polypropyleneoxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; the C₁-C₄ alkyl celluloses and C₄ hydroxyalkylcelluloses, see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.;and the methyl cellulose ethers having an average degree of substitution(methyl) per anhydroglucose unit from about 1.6 to about 2.3 and asolution viscosity of from about 80 to about 120 centipoise measured at20° C. as a 2% aqueous solution. Such materials are available asMETOLOSE SM 100 and METOLOSE SM200, which are the trade names of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRA's include: (I) nonionic terephthalates usingdiisocyanate coupling agents to link polymeric ester structures, seeU.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918Lagasse et al.; and (II) SRA's with carboxylate terminal groups made byadding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With the proper selection of catalyst,the trimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimelliticanhydride rather than by opening of the anhydride linkage. Eithernonionic or anionic SRA's may be used as starting materials as long asthey have hydroxyl terminal groups which may be esterified. See U.S.Pat. No. 4,525,524 Tung et al. Other classes include: (III) anionicterephthalate-based SRA's of the urethane-linked variety, see U.S. Pat.No. 4,201,824, Violland et al.;

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the components orcompositionss of the invention include perfumes, colours and fillersalts, with sodium sulfate being a preferred filler salt.

Highly preferred compositions contain from about 2% to about 10% byweight of an organic acid, preferably citric acid. Also, preferablycombined with a carbonate salt, minor amounts (e.g., less than about 20%by weight) of neutralizing agents, buffering agents, phase regulants,hydrotropes, enzyme stabilizing agents, polyacids, suds regulants,opacifiers, anti-oxidants,.bactericides and dyes, such as thosedescribed in U.S. Pat. No. 4,285 841 to Barrat et al., issued Aug. 25,1981 (herein incorporated by reference), can be present.

Form of the Components or Compositionss

The components or compositions herein can take a variety of physicalforms including liquid and solid forms such as tablet, flake, pastilleand bar, and preferably granular forms. The components or compositionscan be made via a variety of methods, depending on their product form.The solid compositions or components can be made by methods such asdry-mixing, agglomerating, compaction, or spray-drying of the variouscompounds comprised in the detergent component, or mixtures of thesetechniques.

It is highly preferred that the cyclic amine based polymers and theanionic cellulose materials herein are present in an intimate mixture.In solid compositins hor components herein, this mixture can be obtainedby any mixing method, including agglomeration. The intimate mixture arepreferably in the form of a compacted, agglomerated or spray driedgranule.

Detergent compositions and components herein preferably have a bulkdensity of from 300 g/liter or even 350 g/liter or 450 g/liter topreferably 1500 g/liter or 1000 g/liter or even to 850 g/liter.

Fabric Laundering Method

The present invention also provides a method for laundering. Such amethod employs contacting these fabrics with an aqueous washing solutionformed from an effective amount of the detergent components orcompositions herein before described or formed from the individualcomponents of such components or compositions. Contacting of fabricswith washing solution will generally occur under conditions of agitationalthough the components or compositions of the present invention mayalso be used to form aqueous unagitated soaking solutions for fabriccleaning and treatment. As discussed above, it is preferred that thewashing solution have a pH of less than about 11.0, preferably it has apH of less than 10.5 and most preferably it has a pH of less than 9.5.An effective amount of a high density liquid or granular detergentcomponents or compositions in the aqueous wash solution in the washingmachine is preferably from about 500 to about 10000 ppm or even 7000ppm, more preferably from about 1000 to about 3000 ppm.

Fabric Conditioning and Softening

The detergent components or compositions herein may also be used totreat and condition fabrics and textiles. Thus, for example, a fabricconditioning components or compositions comprising the cyclic aminebased polymers and anionic cellulose polymers as described herein, maybe added during the rinse cycle of a conventional home launderingoperation in order to impart the desired fabric appearance and integritybenefits hereinbefore described. Then, preferably at least about 1%,preferably from about 10%, more preferably from about 20% to about 80%,more preferably to about 60% by weight, of the composition or componentis one or more fabric softener actives, such as cationically chargedhydrocarbons, such as C12-C22 dialkyl substitued quaternary ammoniumsalts and/or clays, optionaly with a flocculating polymer.

Alternatively, the composition or component herein may be present in orin the form of a softening and cleaning composition, such as for exampledescribed in EP-B1-313146 and

WO93/01267, preferably comprising additional softening ingredients, suchas clay and optionally a flocculating polymer.

Abbreviations used in the effervescence component and detergentcomposition examples LAS: Sodium linear C11-13 alkyl benzene sulfonateLAS (I): Potassium linear or branched C11-13 alkyl benzene sulfonateTAS: Sodium tallow alkyl sulfate CxyAS: Sodium C1x-C1y alkyl sulfateC46SAS: Sodium C14-C16 secondary (2,3) alkyl sulfate CxyEzS: SodiumC1x-C1y alkyl sulfate condensed with z moles of ethylene oxide CxyEz:C1x-C1y predominantly linear primary alcohol condensed with an averageof z moles of ethylene oxide QAS: R2.N+(CH3)2(C2H4OH) with R2 = C12-C14alkyl QAS 1: R2.N+(CH3)2(C2H4OH) with R2 = C8-C11 alkyl QASA:R2.R3.N+(CH3)2 with R2 and R3 independently being C12-C24 alkyl QASA 1:R2.N+(R1)3 with R2 being C16-C24 alkyl and R1 being C1-C4 alkyl APA:C8-C10 amido propyl dimethyl amine Soap: Sodium linear alkyl carboxylatederived from an 80/20 mixture of tallow and coconut fatty acids STS:Sodium toluene sulphonate CFAA: C12-C14 (coco) alkyl N-methyl glucamideTFAA: C16-C18 alkyl N-methyl glucamide TPKFA: C12-C14 topped whole cutfatty acids STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodiumpyrophosphate Zeolite A: Hydrated sodium aluminosilicate of formulaNa12(AlO2SiO2)12.27H2O having a primary particle size in the range from0.1 to 10 micro- meters (weight expressed on an anhydrous basis)NaSKS-6: Crystalline layered silicate of formula d-Na2Si2O5 Citric acidI: Anhydrous citric acid, 80% having a particle size of from 40 micronsto 70 microns, and having a volume median particle size of 55 micronsCitric acid II: Anhydrous or monohydrate citric acid, 80% having aparticle size of from 15 microns to 40 microns, having a volume averageparticle size of 25 microns Maleic acid: Anhydrous malic acid, 80%having a particle size of from 50 microns to 100 microns, having avolume median particle size of 75 microns Malic acid: Anhydrous maleicacid Tartaric acid: Anhydrous tartaric acid Carbonate: Anhydrous sodiumcarbonate Bicarbonate: Anhydrous sodium bicarbonate Silicate: Amorphoussodium silicate (SiO2:Na2O = 2.0:1) Sulfate: Anhydrous sodium sulfate Mgsulfate: Anhydrous magnesium sulfate Citrate: Tri-sodium citratedihydrate of activity 86.4% with a particle size distribution between425 μm and 850 μm MA/AA: Copolymer of 1:4 maleic/acrylic acid, averagemolecular weight about 70,000 MA/AA (1): Copolymer of 4:6 maleic/acrylicacid, average molecular weight about 10,000 AA: Sodium polyacrylatepolymer of average molecular weight 4,500 CABP: Cyclic amine basedpolymer as described in PCT/US98/19143 and PCT/US98/19141 in examples 1and 2 in table HMC 1: Hydrophobically modified cellulose having an estergroup comprising 14-18 carbon atoms AC: Hydrophobically modified amidecellulose having an amide group comprising 2 to 12 carbon atoms CMC:Sodium carboxymethyl cellulose Cellulose ether: Methyl cellulose etherwith a degree of poly- merization of 650 available from Shin EtsuChemicals Protease: Proteolytic enzyme, having 3.3% by weight of activeenzyme, sold by NOVO Industries A/S under the tradename SavinaseProtease 1: Proteolytic enzyme, having 4% by weight of active enzyme, asdescribed in WO 95/10591, sold by Genencor Int. Inc. Alcalase:Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVOIndustries A/S Cellulase: Cellulytic enzyme, having 0.23% by weight ofactive enzyme, sold by NOVO Industries A/S under the tradename CarezymeAmylase: Amylolytic enzyme, having 1.6% by weight of active enzyme, soldby NOVO Industries A/S under the tradename Termamyl 120T Lipase:Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVOIndustries A/S under the tradename Lipolase Lipase (1): Lipolyticenzyme, having 2.0% by weight of active enzyme, sold by NOVO IndustriesA/S under the tradename Lipolase Ultra Endolase: Endoglucanase enzyme,having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4:Particle containing sodium perborate tetra- hydrate of nominal formulaNaBO2.3H2O PB1: Particle containing anhydrous sodium perborate bleach ofnominal formula NaBO2.H2O2 Percarbonate: Particle containing sodiumpercarbonate of nominal formula 2Na2CO3.3H2O2 NOBS: Particle comprisingnonanoyloxybenzene sulfonate in the form of the sodium salt, theparticles having a weight average particle size of 750 microns to 900microns NAC-OBS: Particle comprising (6-nonamidocaproyl) oxybenzenesulfonate, the particles having a weight average particle size of from825 microns to 875 microns TAED: Tetraacetylethylenediamine DTPA:Diethylene triamine pentaacetic acid DTPMP: Diethylene triaminepenta(methylene phosphonate), marketed by Monsanto under the TradenameDequest 2060 Photoactivated: Sulfonated zinc phthlocyanine encapsulatedin bleach (1) dextrin soluble polymer Photoactivated: Sulfonated aluminophthlocyanine encapsulated in bleach (2) dextrin soluble polymerBrightener 1: Disodium 4,4′-bis(2-sulphostyryl)biphenyl Brightener 2:Disodium 4,4′-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)stilbene-2:2′- disulfonate EDDS:Ethylenediamine-N,N′-disuccinic acid, (S, S) isomer in the form of itssodium salt. HEDP: 1,1-hydroxyethane diphosphonic acid PEGx:Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO:Polyethylene oxide, with an average molecular weight of 50,000 TEPAE:Tetraethylenepentaamine ethoxylate PVI: Polyvinyl imidosole, with anaverage molecular weight of 20,000 PVP: Polyvinylpyrolidone polymer,with an average molecular weight of 60,000 PVNO: PolyvinylpyridineN-oxide polymer, with an average molecular weight of 50,000 PVPVI:Copolymer of polyvinylpyrolidone and vinylimidazole, with an averagemolecular weight of 20,000 QEA: bis((C2H5O)(C2H4O)n)(CH3)-N+-C6H12-N+-(CH3) bis((C2H5O)—(C2H4O))n, wherein n = from 20 to 30 SRP: Anionicallyend capped poly esters PEI: Polyethyleneimine with an average molecularweight of 1800 and an average ethoxylation degree of 7 ethyleneoxyresidues per nitrogen Silicone antifoam: Polydimethylsiloxane foamcontroller with siloxane-oxyalkylene copolymer as dispersing agent witha ratio of said foam controller to said dispersing agent of 10:1 to100:1 Opacifier: Water based monostyrene latex mixture, sold by BASFAkiengesellschaft under the trade- name Lytron 621 Wax: Paraffin wax

Effervescence granule: any of the effervescence granules I to XII

The following effervescence granules I to XII are in accord with theinvention (ingredients in % by weight of effervescence granule). Thegranules can be prepared by mixing the ingredeints and agglomerating theingredients or by compacting the mixed ingredients, the later being thepreffered process for preparing particle I, IV and VIII.

In the following examples all levels are quoted as % by weight of thecomposition:

TABLE I The following compositions are in accordance with the invention.A B C D E F G H I Spray-dried Granules LAS 10.0 10.0 15.0 5.0 5.0 10.0 —— — TAS — 1.0 — — — — MBAS — — 5.0 5.0 — — — C₄₅AS — — 1.0 2.0 2.0 — — —C₄₅AE₃S — — 1.0 — — — QAS or QAS 1 1.0 1.5 1.0 1.0 0.5 0.8 0.8 1.2 2.0HMC 0.3 0.8 1.5 1.0 0.9 1.3 0.5 1.5 4.0 MgSO4 0.5 0.5 0.1 — — — — Sodiumcitrate — — — 3.0 5.0 — — — Sodium carbonate 10.0 7.0 15.0 10.0 — — —Sodium sulphate 5.0 5.0 — — 5.0 3.0 — — — Sodium silicate 1.6R — — — —2.0 — — — Zeolite A 16.0 18.0 20.0 20.0 — — — — — SKS-6 — — — 3.0 5.0 —— — — MA/AA or AA 1.0 2.0 11.0 — — 2.0 — — — PEG 4000 — 2.0 — 1.0 — 1.0— — — QEA 1.0 — — — 1.0 — 0.5 — Brightener 0.05 0.05 0.05 — 0.05 — — — —Silicone oil 0.01 0.01 0.01 — — 0.01 — — — Agglomerate LAS — — — — 2.02.0 — MBAS — — — — — — 1.0 C₄₅AS — — — — 2.0 — — AE₃ — — — — — 1.0 0.5Carbonate — — 4.0 1.0 1.0 1.0 — Sodium citrate — — — — — — 5.0 CFAA — —— — — Citric acid — — — 4.0 — 1.0 1.0 QEA — — — 2.0 2.0 — — SRP — — —1.0 1.0 0.2 — Zeolite A — — — 15.0 26.0 15.0 16.0 Sodium silicate — — —— — — — PEG — — — — — — 4.0 — — Builder Agglomerates SKS-6 6.0 — — — 6.03.0 — 7.0 10.0 LAS 4.0 5.0 — — 5.0 3.0 — 10.0 12.0 Dry-add particulatecomponents effervescence granule — 4.0 10.0 4.0 25 8.0 12.0 2.0 4.0 QEA— — — 0.2 0.5 — — — — NACAOBS 3.0 — — 4.5 — — — 2.5 — NOBS 1.0 3.0 3.0 —— — — — 5.0 TAED I 2.5 — — 1.5 2.5 6.5 — 1.5 — MBAS — — — 8.0 — — 8.0 —4.0 LAS (flake) 10.0 10.0 — — — — — 8.0 — Citric acid II — — — Spray-onBrightener 0.2 0.2 0.3 0.1 0.2 0.1 — 0.6 0.3 Dye — — — 0.3 0.05 0.1 — —— AE7 — — — — — 0.5 — 0.7 — Perfume 1.0 0.5 1.1 0.8 0.3 0.5 0.3 0.5 —Dry-add Citrate — — 20.0 4.0 — 5.0 15.0 — 5.0 Percarbonate 15.0 3.0 6.010.0 — — 24.0 18.0 5.0 Perborate — — — — 6.0 18.0 — — — Photobleach 0.020.02 0.02 0.1 0.05 — 0.3 — 0.03 Enzymes (cellulase, amylase, protease,lipase) 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 Carbonate 0.0 10.0 — — —5.0 8.0 10.0 5.0 Perfume (encapsulated) — 0.5 0.5 — 0.3 — 0.2 — — Sudssuppressor 1.0 0.6 0.3 — 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 —— 0.3 — Citric acid (I or coarse) — — — 6.0 6.0 — — — 5.0 Dyed carbonate(blue, green) 0.5 0.5 1.0 2.0 — 0.5 0.5 0.5 1.0 SKS-6 — — — 4.0 — — —6.0 — Fillers up to 100%

TABLE II The following compositions are in accordance with theinvention. A B C D E F G H I Spray-Dried Granules LAS or LAS (I) 10.010.0 16.0 5.0 5.0 10.0 — — — TAS — 1.0 — — — — MBAS — — — 5.0 5.0 — — —C₄₅AS — — 1.0 2.0 2.0 — — — C₄₅AE₃S — — — 1.0 — — — QAS or QAS 1 1.0 0.81.0 1.0 2.0 4.0 1.0 0.5 0.8 DTPA, HEDP and/or EDDS 0.3 0.3 0.3 0.3 — — —MgSO4 0.5 0.4 0.1 — — — — Sodium citrate 10.0 12.0 17.0 3.0 5.0 — — —Sodium carbonate 15.0 8.0 15.0 10.0 — — — Sodium sulphate 5.0 5.0 — —5.0 3.0 — — — Sodium silicate 1.6R — — — — 2.0 — — — Zeolite A — — — 2.0— — — — — SKS-6 — — — 3.0 5.0 — — — — MA/AA or AA 1.0 2.0 10.0 — — 2.0 —— — PEG 4000 — 2.0 — 1.0 — 1.0 — — — QEA 1.0 — — — 1.0 — — — 0.5Brightener 0.05 0.05 0.05 — 0.05 — — — — Silicone oil 0.01 0.01 0.01 — —0.01 — — — HMC 0.5 1.2 2.0 1.5 3.0 4.0 0.6 1.6 1.0 Agglomerate LAS — — —— — — 2.0 2.0 — MBAS — — — — — — — — 1.0 C₄₅AS — — — — — — 2.0 — — CABP— — — — — 1.0 0.2 — 0.5 Carbonate — — — — 4.0 1.0 1.0 1.0 — Sodiumcitrate — — — — — — — — 5.0 CFAA — — — — — — — — Citric acid — — — — —4.0 — 1.0 1.0 QEA — — — — — 2.0 2.0 1.0 — SRP — — — — — 1.0 1.0 0.2 —Zeolite A — — — — — 15.0 26.0 15.0 16.0 Sodium silicate — — — — — — — —— PEG — — — — — — 4.0 — — TAED II 3.0 1.5 Builder Agglomerate SKS-6 6.05.0 — — 6.0 3.0 — 7.0 10.0 LAS 4.0 5.0 — — 5.0 3.0 — 10.0 12.0 Dry-addparticulate components Effervescence granule — 10.0 4.0 5 15 8.0 2.0 204.0 NACAOBS 3.0 — — 1.5 — — — 5.5 — NOBS/LOBS/DOBS — 3.0 3.0 — — — — —5.0 TAED I 2.5 — — 1.5 2.5 6.5 — 1.5 — HMC — — — 0.7 — — 1.0 — 0.5 LAS(flake) — — — — — — — 8.0 — Spray-on Brightener 0.2 0.2 0.3 0.1 0.2 0.1— 0.6 — Dye — — — 0.3 0.05 0.1 — — — AE7 — — — — — 0.5 — 0.7 — Perfume —— — 0.8 — 0.5 0.8 0.5 1.0 Dry-add QEA — — — 0.2 0.5 — — — — Citrate 4.0— 3.0 4.0 — 5.0 15.0 — 5.0 Percarbonate 15.0 3.0 6.0 10.0 — — 12.0 18.05.0 Perborate — — — — 6.0 18.0 — — — Photobleach 0.02 0.02 0.02 0.1 0.05— 0.3 — 0.03 Enzymes (cellulase, amylase, protease, lipase) 1.5 0.3 0.50.5 0.8 2.0 0.5 0.16 0.2 Carbonate II — — — — — 5.0 8.0 10.0 5.0 Perfume(encapsulated) 0.6 0.5 0.5 — 0.3 0.5 0.2 0.1 0.6 Suds suppressor 1.0 0.60.3 — 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 — — 0.3 — Citricacid II — — — — — — — 5.0 5.0 Dyed carbonate (blue, green) 0.5 0.5 ? 2.0— 0.5 0.5 0.5 1.0 SKS-6 — — — 4.0 — — — 6.0 — Fillers up to 100%

TABLE III The following are high density and bleach-containing detergentformulations according to the present invention: A B C Blown PowderZeolite A — — 15.0 QASA — 2.5 — LAS 3.0 — 3.0 C45AS 3.0 2.0 4.0 QAS — —1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 HMC 2.0 — 1.5CABP 0.8 1.0 0.5 Agglomerates HMC 2.0 2.0 1.0 QAS 1.0 — — LAS — 11.0 7.0TAS 2.0 2.0 1.0 Silicate 3.0 — 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.08.0 4.0 Agglomerate NaSKS-6 (I) or (II) 15.0 12.0 5.0 LAS 8.0 7.0 4.0 AS5.0 — — Spray On Perfume 0.3 0.3 0.3 C25E3 2.0 — 2.0 brightener 0.1 0.4photobleach 0.03 0.05 — Dry additives QEA 1.0 2.0 — Citric acid I 5.0 —2.0 Bicarbonate I — 3.0 — Carbonate II 8.0 15.0 10.0 NAC OBS 6.0 — 5.0Manganese catalyst — — 0.3 TAED I 3.0 — NOBS — 2.0 — Percarbonate 14.07.0 10.0 Polyethylene oxide of MW 5,000,000 — — 0.2 Bentonite clay — —10.0 effervescence granule — 5.5 7.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.40.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.05.0 CMC 1.0 0.5 1.0 Balance (Moisture and Miscellaneous) 100.0 100.0100.0 Density (g/liter) 850 850 850

TABLE IV The following liquid composition is in accord with theinvention Component Wt. % Wt. % Wt. % Wt. % C₁₂₋₁₅ alkyl ether (2.5)sulfate 38 38 38 38 C₁₂ glucose amide 6.86 6.86 6.86 6.86 Citric Acid4.75 4.75 4.75 4.75 C₁₂₋₁₄ Fatty Acid 2.00 2.00 2.00 2.00 Enzymes 1.021.02 1.02 1.02 MEA 1.0 1.0 1.0 1.0 Propanediol 0.36 0.36 0.36 0.36 Borax6.58 6.58 6.58 6.58 Dispersant 1.48 1.48 1.48 1.48 Na Toluene Sulfonate6.25 6.25 6.25 6.25 QAS or QAS 1 1.0 1.0 — 1.0 QASA or QASA 1 2.0 2.02.0 — QEA or CABP — — 1.0 0.5 HMC 0.5 1.8 2.0 0.8 CMC or AC 1.0 1.0 2.0— Dye, Perfume, Brighteners, Balance Balance Balance BalancePreservatives, Suds Suppressor, Other Minors, Water 100% 100% 100% 100%

TABLE V The following liquid detergent formulations are preparedaccording to the present invention A B C D E LAS 11.5 9.0 — 4.0 —C25E2.5S — 3.0 18.0 — 16.0 C45E2.25S 11.5 3.0 — 16.0 — C23E9 — 3.0 2.02.0 1.0 C23E7 3.2 — — — — CFAA — — 5.0 — 3.0 TPKFA 2.0 — 2.0 0.5 2.0Citric (50%) 6.5 1.0 2.5 4.0 2.5 Ca formate 0.1 0.06 0.1 — — Na formate0.5 0.06 0.1 0.05 0.05 STS 4.0 1.0 3.0 1.2 — Borate 0.6 — 3.0 2.0 3.0 Nahydroxide 6.0 2.0 3.5 4.0 3.0 Ethanol 2.0 1.0 4.0 4.0 3.0 1,2Propanediol 3.0 2.0 8.0 8.0 5.0 Monoethanol- 3.0 1.5 1.0 2.5 1.0 amineHMC 2.0 1.0 1.0 3.0 0.4 QAS 1 or QAS — 1.0 2.0 0.8 1.0 Protease 0.030.01 0.03 0.02 0.02 Lipase — — 0.002 — — Amylase — — — 0.002 — Cellulase— — 0.0002 0.0005 0.0001 CMC 0.2 — 0.5 — 1.0 DTPA — — 0.3 — — PVNO — —0.3 — 0.2 QASA or 0.9 1.7 0.5 — QASA 1 Silicone anti- 0.04 0.02 0.1 0.10.1 foam Miscellaneous and water

TABLE VI The following liquid detergent formulations are according tothe present invention A B C D E F G H LAS 10.0 13.0 9.0 — 25.0 — — —C25AS 4.0 1.0 2.0 10.0 — 13.0 18.0 15.0 C25E3S 1.0 — — 3.0 — 2.0 2.0 4.0C25E7 6.0 8.0 13.0 2.5 — — 4.0 4.0 TFAA — — — 4.5 — 6.0 8.0 8.0 APA —1.4 — — 3.0 1.0 2.0 — TPKFA 2.0 — 13.0 7.0 — 15.0 11.0 11.0 Citric 2.03.0 1.0 1.5 1.0 1.0 1.0 1.0 Dodecenyl/tetradecenyl succinic acid 12.010.0 — — 15.0 — — — Rapeseed fatty acid 4.0 2.0 1.0 — 1.0 — 3.5 —Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.06.0 8.0 10.0 13.0 Monoethanolamine — — — 5.0 — — 9.0 9.0 Triethanolamine— — 8.0 — — — 0.4 0.3 HMC 0.2 2.0 0.5 0.7 2.0 1.2 1.0 4.0 QAS or QAS 10.3 0.4 0.5 1.0 1.0 2.0 0.5 1.0 QASA 1.0 1.0 0.5 0.5 1.0 Carbohydrase0.08 0.02 0.01 0.02 Protease 0.02 0.02 0.01 .008 — — .003 .003 Lipase —.002 — .002 .004 0.01 0.01 0.01 Amylase .004 .004 0.01 .008 — — .004.003 Cellulase — — — .002 — — 0.2 0.1 QEA or CABP 0.3 — 0.3 — 1.0 1.5 —— Boric acid 0.1 0.2 1.0 2.0 4.0 4.0 — — Ca chloride — 0.02 — 0.01 0.10.2 0.3 — Brightener 1 — 0.4 — — 0.4 — — — Suds suppressor 0.1 0.3 — 0.10.8 0.7 — — Opacifier 0.5 0.4 — 0.3 8.0 7.5 8.0 8.2 NaOH up to pH 8.08.0 7.6 7.7 Miscellaneous and water

What is claimed is:
 1. A detergent composition or component comprising:a) from 0.01% to 90% by weight of a salt of a quatemary ammoniumcompound; and b) from 0.01%to 90% by weight of a hydrophobicallymodified cellulosic polymer, wherein the quaternary ammonium compoundand the hydrophobically modified cellulosic material are in the form ofan agglomerate, a compacted granule a spray dried granule, or a mixturethereof.
 2. A detergent composition or component according to claim 1wherein the cellulosic polymer is of the formula

wherein each R is selected from the group consisting of R₂, R_(C), and

wherein: each R₂ is independently selected from the group consisting ofH and C₁-C₄ alkyl; each R_(C) is

 wherein each Z is independently selected from the group consisting ofM, R₂, R_(C), and R_(H); each R_(H) is independently selected from thegroup consisting of C₅-C₂₀ alkyl, C₅-C₇ cycloalkyl, C₇-C₂₀ alkylaryl,C₇-C₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, C₁-C₂₀alkoxy-2-hydroxyalkyl, C₇-C₂₀ alkylaryloxy-2-hydroxyalkyl, (R₄)₂N-alkyl,(R₄)₂N-2-hydroxyalkyl, (R₄)₃N-alkyl, (R₄)₃N-2-hydroxyalkyl, C₆-C₁₂aryloxy-2-hydroxyalkyl,

each R₄ is independently selected from the group consisting of H, C₁-C₂₀alkyl, C₅-C₇ cycloalkyl, C₇-C₂₀ alkylaryl, C₇-C₂₀ arylalkyl, aminoalkyl,alkylaminoalkyl, dialkylaminolalkyl, piperidinoalkyl, morpholinoalkyl,cycloalkylaminoalkyl and hydroxyalkyl; each R₅ is independently selectedfrom the group consisting of H, C₁-C₂₀ alkyl, C₅-C₇ cycloalkyl,(R₄)₂N-alkyl, and (R₄)₃N-alkyl; wherein: M is a suitable cation selectedfrom the group consisting of Na, K, 1/2Ca, and 1/2Mg; each x is from 0to 5; each y is from 1 to 5; and provided that: the Degree ofSubstitution for group R_(H) is between 0.001 and 0.1; the Degree ofSubstitution for group R_(C) wherein Z is H or M is between 0.2 and 2.0;if any R_(H) bears positive charge, it is balanced by a suitable anion;and two R₄×on the same nitrogen can together form a ring structureselected from the group consisting of piperidine and morpholine.
 3. Acomposition or component according to claim 2, wherein each R_(H) isindependently selected from the group consisting of C₅-C₂₀ alkyl, C₅-C₇cycloalkyl, C₇-C₂₀ alkylaryl, C₇-C₂₀ arylalkyl, substituted alkyl,hydroxyalkyl, C₁-C₂₀ alkoxy-2-hydroxyalkyl, C₇-C₂₀alkylaryloxy-2-hydroxyalkyl, (R₄)₂N-alkyl, (R₄)₂N-2-hydroxyalkyl,(R₄)₃N-alkyl, (R₄)₃N-2-hydroxyalkyl, and C₆-C₁₂ aryloxy-2-hydroxyalkyl.4. A composition or component according to claim 2, wherein each R_(H)is independently selected from the group consisting of


5. A detergent component or composition according to claim 1 wherein thequaternary ammonium compound is selected from quaternary ammoniumsurfactants, quaternary ammonium softeners, quaternary ammoniumdispersants and mixtures thereof.
 6. A component or compositionaccording claim 5 comprising a cationic surfactant containing at least aquatemary mono-alkoxylated ammonium surfactants.
 7. A opposition orcomponent according to claim 5 whereby the quaternary ammonium compoundor compounds and the cellulosic polymer are in an intimate mixture withone another.
 8. A detergent component according to claim 1 obtainable bya process comprised of the steps of mixing the cellulosic polymer andthe quaternary ammonium compound or compounds to form an intimatemixture and agglomerating the intimate mixture.
 9. A laundry compositionor component according to claim 1 which also comprises a cyclic aminebased polymer.